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WO2006045570A1 - Method for producing a steel sheet protected against corrosion - Google Patents

Method for producing a steel sheet protected against corrosion Download PDF

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Publication number
WO2006045570A1
WO2006045570A1 PCT/EP2005/011387 EP2005011387W WO2006045570A1 WO 2006045570 A1 WO2006045570 A1 WO 2006045570A1 EP 2005011387 W EP2005011387 W EP 2005011387W WO 2006045570 A1 WO2006045570 A1 WO 2006045570A1
Authority
WO
WIPO (PCT)
Prior art keywords
cooling
steel sheet
cooling medium
aqueous
coated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2005/011387
Other languages
German (de)
French (fr)
Inventor
Monika Riemer
Ingo Rogner
Bernd Schuhmacher
Christian Schwerdt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp Steel Europe AG
Original Assignee
ThyssenKrupp Steel AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ThyssenKrupp Steel AG filed Critical ThyssenKrupp Steel AG
Priority to AU2005298896A priority Critical patent/AU2005298896A1/en
Priority to US11/577,981 priority patent/US20100040783A9/en
Priority to EP05796770A priority patent/EP1805342A1/en
Priority to JP2007538319A priority patent/JP2008518100A/en
Priority to BRPI0517630-1A priority patent/BRPI0517630A/en
Publication of WO2006045570A1 publication Critical patent/WO2006045570A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment

Definitions

  • the invention relates to a method for producing a corrosion-protected steel sheet for coating with an organic coating agent, in which the coated with a coating of zinc or a zinc alloy corrosion-protected steel sheet in vacuum coated with at least one additional metal or metal alloy, then a thermal
  • the galvanizing of steel body panels for the purpose of corrosion protection has largely prevailed in the last decades.
  • the galvanized steel plates in the hot dip process or by means of electrolytic deposition are characterized by a good adhesion of the zinc layer to the steel sheet / and a good processability, in particular Umformbarköit from.
  • DE 100 39 375 A1 describes a process for producing a corrosion-protected steel sheet, in which a layer of metals, in particular alkaline earth metals, magnesium or aluminum or their alloys, in a continuous steel sheet provided with a zinc or zinc alloy coating
  • this heat treatment which consists of a heating and a holding phase, it comes in the areas of the surface in which in the vacuum coating multiphase alloys between the vapor-deposited layer and the zinc or zinc alloy layer with a melting temperature lower than that of the zinc or zinc alloy layer, locally to the welds, in which case the vapor-deposited metal or vapor-deposited alloy also penetrates into deeper layers of the zinc coating heat treatment is the steel sheet in cooled an unchanged oxygen-poor atmosphere, the fusions solidify.
  • the corrosion resistance of the galvanized steel sheet is positively influenced by the dissolution of the Zinküberzmgs is slowed down by the stabilizing effect of the vapor deposited and penetrated by the melts ia the zinc coating metal greatly.
  • DE 195 27 515 C1 describes another method for producing a corrosion-protected steel sheet.
  • one or more of Zirxk different metals, in particular Fe, Mn, Cu, Ni and Mg, or their alloys by vacuum coating applied to a provided with a zinciferous steel sheet and then without intermediate exposure to oxidizing atmosphere of a thermal
  • the invention is therefore based on the object of specifying a method for producing a corrosion-protected steel sheet for coating with an organic coating agent, which in comparison to the generic state of the art by excellent adhesion of the organic coating composition and by a high corrosion resistance in the coated state of the sheet distinguished.
  • the object is achieved by a method according to the preamble of claim 1, characterized in that the cooling is carried out with an aqueous cooling medium under normal atmospheric conditions.
  • a steel sheet is first provided in a known manner with a coating of zinc or a Zinklegieri ⁇ ng. This takes place in a known manner in the melt-dip process (hot-dip galvanizing) or by electrolytic deposition.
  • the galvanized steel sheet is coated in vacuum with an additional metal.
  • a thermal diffusion treatment in which atoms of the metal layer applied in a vacuum diffuse into the underlying zinc or zinc alloy. Due to the residual gas content in the vacuum and during the thermal diffusion treatment, a native oxide layer forms on the surface of the coated steel sheet, which passivates the surface and thus increases its corrosion resistance.
  • the "finished steel sheet after the thermal diffusion treatment is cooled with an aqueous cooling medium.
  • Another advantage of cooling by means of an aqueous cooling medium is that in subregions of the coated surface, in which no native oxide layer is formed, ie where the bare metallic coating is exposed, water molecules are decomposed from the coolant, with anti-corrosive, partially form sparingly soluble hydroxides. These hydroxides or: the resulting oxides in the subsequent drying improve significantly the adhesion of organic coatings on the surface of the steel sheet.
  • the applied in vacuum on the galvanized sheet surface layer may be composed of one or more metals.
  • those metals are used which form mixed phases with the zinc of the zinc or zinc alloy layer. This results in a good connection of both layers, and the corrosion resistance is increased.
  • Particularly suitable are reactive metals, such as magnesium, aluminum, iron or manganese or their alloys.
  • a predetermined temperature control in the sense of a defined starting temperature of the finished steel sheet zi ⁇ onset of cooling, a preset temperature of the cooling medium and a specified cooling time sowor ⁇ l shortening the treatment time and the quality of the corrosion protection layer can be improved in terms of higher corrosion resistance.
  • the starting temperature of the steel sheet at the beginning of Abkühlumg is preferably 250 to 35O 0 C, in particular 290 to 310 0 C.
  • the setting of the starting temperature can technically! done in different ways.
  • the use of cooling rolls is just as possible as the use of gas cooling.
  • the duration of the cooling is preferably 1 to LO s.
  • the temperature of the cooling medium should not be set too high, since in this case the metal coating of the steel sheet by the coolant is strong is attacked.
  • the temperature of the coolant should not exceed 42 ° C.
  • the final temperature of the steel sheet after cooling is preferably 20 b> is 120 0 C, in particular 40 to 60 0 C. This results in a wide working range. An increase in the final temperature beyond 12O 0 C addition does not make sense, otherwise it can lead to damage of subsequent rubberized rollers for the removal of the cooling medium.
  • the cooling can be carried out in a dip.
  • the coated steel sheet can also be sprayed, wherein the spraying is preferably carried out under high pressure, since in this case a particularly rapid cooling and Passivierrung the surface can be achieved.
  • hot sheet metal surfaces in this way are formed directly on the OberfLowne forming Wasserschampfschichit which greatly reduces the heat transfer between the steel sheet and the cooling medium (Leidenfrost effect).
  • aqueous cooling medium should be removed immediately after cooling from the surface of the coated steel sheet.
  • the removal of the cooling medium can be done by squeezing or durrch a gas jet.
  • the corrosion resistance and the adhesion of the organic coating to be applied can be further improved by further measures.
  • soluble salts can be added to the aqueous cooling medium. These set free suitable divalent metal ions or hydroxide ions and thus shift the solution equilibrium to the undissociated oxide according to the equation
  • buffering substances in particular acetate, phosphate, borate, carbonate, or citrate ions, can be added to the aqueous cooling medium, by means of which an optimum pH in the sense of minimum hydrolysis of amphoteric native metal oxides can be set.
  • the pH value should be neither in the weakly acidic range (pH ⁇ 5) nor in the strongly basic range (pH> 12.5).
  • the drawing shows a plant for the continuous refining and subsequent painting of a steel strip.
  • a substrate in the form of a steel strip 1 is first passed through one or more cells 2 and coated in a electrolytic deposition process with a zinc layer.
  • galvanizing in the hot dip process is possible.
  • the steel strip 1 enters a Vakuumkanxmer 3 a.
  • the band 1 with one from the state coating technique known in the art, for example by means of PVD, with an additional metal, preferably magnesium coated.
  • additional metal preferably magnesium coated.
  • Further usable metals are, for example, aluminum and manganese.
  • the coated galvanized steel strip 1 After leaving the vacuum chamber 3, the coated galvanized steel strip 1 enters a heating chamber 4 provided with a heating device 4a. In this heating chamber 4 then takes place a thermal diffusion treatment, which can be carried out in a normal atmosphere. In the course of the diffusion treatment, the magnesium layer applied in a vacuum partially diffuses into the underlying zinc layer, forming intermetallic phases consisting of zinc and magnesium.
  • the steel strip 1 After emerging from the heating chamber 4, the steel strip 1 is deflected at least one cooling roller 5 and is thereby cooled to a defined temperature. This is at the same time the starting temperature of the subsequent cooling process and is preferably 250 to 350 0 C, in particular 290 to 31O 0 C.
  • the steel strip 1 is passed into a further chamber 6.
  • the diffusion-treated surface with an aqueous Spray cooling medium under high pressure.
  • the cooling can also take place in a dipping bath.
  • the aqueous cooling medium may be pure Wasserr act.
  • salts which shift the solution equilibrium to the undissociated oxide can also be dissolved in the cooling medium.
  • the cooling medium can contain buffering substances, for example acetate, phosphate, borate, carbonate, or citrate ions, by means of which an optimum pH value can be set in the sense of minimal hydrolysis of magnetic native metallic oxides.
  • the spraying device is designed such that the coated steel sheet is completely wetted immediately at the beginning of the cooling by the aqueous cooling medium in order to avoid the formation of visible patterns on the surface.
  • the cooling in the chamber 6 takes place with a predetermined temperature control. Daloei is the temperature of the cooling medium maximum 42 0 C-
  • the exposure time of the cooling medium to the steel strip 1 is between 1 and 10 s.
  • the cooling medium is removed by squeezing rollers 7 from the Bandoberiflache.
  • the residual heat of the belt 1 supports the removal of the cooling medium by evaporation.
  • the removal of the cooling medium can also be effected by a gas jet.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Electrochemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention relates to a method for producing a steel sheet (1) which is protected against corrosion and coated with an organic coating agent. According to said method, the steel sheet (1) protected against corrosion by means of a zinc or zinc alloy coating is coated in a vacuum with at least one additional metal or metal alloy, subjected to a thermal diffusion treatment, and then cooled. The inventive method is characterised in that the steel sheet is cooled by an aqueous cooling medium.

Description

Verfahren zum Herstellen eines korrosionsgeschützten StahlblechsMethod for producing a corrosion-protected steel sheet

Die Erfindung betrifft ein Verfahren zum Herstellen eines korrosionsgeschützten Stahlblechs zur Beschichtung mit einem organischen BeSchichtungsmittel, bei dem das mit: einem Überzug aus Zink oder einer Zinklegierung korrosionsgeschützte Stahlblech im Vakuum mit mindest ens einem zusätzlichen Metall oder einer Metalllegierung beschichtet, anschließend einer thermischenThe invention relates to a method for producing a corrosion-protected steel sheet for coating with an organic coating agent, in which the coated with a coating of zinc or a zinc alloy corrosion-protected steel sheet in vacuum coated with at least one additional metal or metal alloy, then a thermal

Diffusionsbehandlung unterworfen und abschließend abg~ekühlt wird.Is subjected to diffusion treatment and finally ABG ekühlt ~.

In der Automobilindustrie besteht großer Bedarf an Werkstoffen mit hoher Korrosionsbeständigkeit und gleichzeitig guten Verarbeitungseigenschaften. Die Verzinkung von Karosserieblechen aus Stahl (Schmelztauchverfahren oder elektrolytische Beschichtung) zum Zwecke des Korrosionsschutzes hat sich in den let zten Jahrzehnten weitgehend durchgesetzt. Die im Schmelztauchverfahren oder mittels elektrolytischer Abscheidung verzinkten Stahlbleche zeichnen sich durch eine gute Haftung der Zinkschicht auf dem Stahlblech/und eine gute Verarbeitbarkeit, insbesondere Umformbarköit, aus.In the automotive industry there is a great need for materials with high corrosion resistance and at the same time good processing properties. The galvanizing of steel body panels (hot dip or electrolytic coating) for the purpose of corrosion protection has largely prevailed in the last decades. The galvanized steel plates in the hot dip process or by means of electrolytic deposition are characterized by a good adhesion of the zinc layer to the steel sheet / and a good processability, in particular Umformbarköit from.

Als Problem erweist sich jedoch regelmäßig die unzureichende Haftung einer organischen Beschichtung, insbesondere einer Lackschicht, auf der Oberfläche de s veredelten Stahlblechs. Durch die Lackschicht dringen Luftsauerstoff und Feuchtigkeit an die Blechoberfläche, welche mit dieser reagieren und somit zu einer fortschreitenden Degradation der Oberfläche führen. Um. dies zu verhindern und somit eine hinreichende Lackhaftung zu gewährleisten, wird das Stahlblech einer zusätzlichen Zwischenbehandlung (z.B. Chromatieren) unterworfen, die einen zusätzlichen Aufwand bedeutet und aufgrund des Einsatzes CrVI-haltiger Substanzen teilweise ökologisch bedenklich sind.As a problem, however, proves the inadequate adhesion of an organic coating, in particular a lacquer layer on the surface de ss refined steel sheet. Through the paint layer, atmospheric oxygen and moisture penetrate the sheet surface, which react with it and thus lead to a progressive degradation of the surface. Around. To prevent this and thus to ensure a sufficient paint adhesion, the steel sheet is subjected to an additional intermediate treatment (eg, chromating), which means an additional expense and due to the use of Cr VI- containing substances are partially environmentally questionable.

Verfahren der eingangs genannten Art sind aus dem Stan_d der Technik bekannt. In der DE 100 39 375 Al ist ein Verfahren zur Herstellung eines korrosionsgeschützten Stahlblech,s beschrieben, bei welchem auf ein mit einem Zink- oder Zinklegierungsüberzug" versehenes Stahlblech eine Schicht aus Metallen, insbesondere Erdalkalimetallen, Magnesium oder Aluminium oder deren Legierungen, in einem kontinuierlichen Prozess durch Vakuumbeschichtung aufgebracht wird. Anschließend wird das beschichtete Blech einer Wärmebehandlung unterworfen. Bei dieser Wärmebehandlung, welche aus einer Aufheiz- und einer Haltephase besteht, kommt es in den Bereichen der Oberfläche, in denen sich bei der Vakuumbeschichtung mehrphasige Legierungen zwischen der aufgedampften Schicht und der Zink- bzw. Zinklegierungsschicht mit einer gegenüber der Zink- bzw. Zinklegierungsschicht geringerer Schmelztemperatur gebildet haben, lokal zu AufSchmelzungen. Dabei dringt das aufgedampfte Metall bzw. die aufgedampfte Legierung auch in tiefere Schichten des Zinküberzugs ein. Im Anschluss an die Wärmebehandlung wird das Stahlbleclh in einer unverändert sauerstoffarmen Atmosphäre abgekühlt, wobei die Aufschmelzungen erstarren.Methods of the type mentioned are known from the Stan_d of the art. DE 100 39 375 A1 describes a process for producing a corrosion-protected steel sheet, in which a layer of metals, in particular alkaline earth metals, magnesium or aluminum or their alloys, in a continuous steel sheet provided with a zinc or zinc alloy coating In this heat treatment, which consists of a heating and a holding phase, it comes in the areas of the surface in which in the vacuum coating multiphase alloys between the vapor-deposited layer and the zinc or zinc alloy layer with a melting temperature lower than that of the zinc or zinc alloy layer, locally to the welds, in which case the vapor-deposited metal or vapor-deposited alloy also penetrates into deeper layers of the zinc coating heat treatment is the steel sheet in cooled an unchanged oxygen-poor atmosphere, the fusions solidify.

Durch dieses Verfahren wird die Korrosionsbeständigkeit des verzinkten Stahlblechs positiv beeinflusst, indem die Auflösung des Zinküberzmgs durch die stabilisierende Wirkung des aufgedampften und durch die Aufschmelzungen ia den Zinküberzug eingedrungenen Metalls stark verlangsamt wird.By this method, the corrosion resistance of the galvanized steel sheet is positively influenced by the dissolution of the Zinküberzmgs is slowed down by the stabilizing effect of the vapor deposited and penetrated by the melts ia the zinc coating metal greatly.

In der DE 195 27 515 Cl ist ein weiteres Verfahren zur Herstellung eines korrosionsgeschützten Stahlblechs beschrieben. Bei diesem wird auf ein mit einem zinkhaltigen Überzug versehenes Stahlfeinblech ein oder mehrere von Zirxk verschiedene Metalle, insbesondere Fe, Mn, Cu, Ni und Mg, oder deren Legierungen durch Vakuumbeschichtung aufgebracht und anschließend ohne zwischenzeitliche Exposition an oxidierender Atmosphäre einer thermischenDE 195 27 515 C1 describes another method for producing a corrosion-protected steel sheet. In this case, one or more of Zirxk different metals, in particular Fe, Mn, Cu, Ni and Mg, or their alloys by vacuum coating applied to a provided with a zinciferous steel sheet and then without intermediate exposure to oxidizing atmosphere of a thermal

Diffusionsbehandlung mit anschließender Abkühlung in einer- Inertgasatmospäre unterzogen. Im Zuge der Diffusionsbehandlung bildet sich an der Oberfläche eine Schicht einer zinkreichen Legierung und zudem Mischphasen mit dem oder den im Vakuum aufgebrachten Metallen aus. Mithilfe dieses Verfahrens ist die Herstellung eines verzinkten Stahlbleches guter Oberflächenqualität und Korrosionsbeständigkeit möglich.Subjected to diffusion treatment followed by cooling in an inert gas atmosphere. In the course of the diffusion treatment, a layer of a zinc-rich alloy forms on the surface and also mixed phases with the metal (s) applied in a vacuum. This process allows the production of a galvanized steel sheet of good surface quality and corrosion resistance.

Bei den aus dem Stand der Technik bekannten Verfahren ist der apparative Aufwand j edoch hoch, da nicht nur die Wärmebehandlung, sondern auch der sich daran anschließende Abkühlungsprozess in einer Inertgasatmosphäre durchzuführen sind. Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren zur Herstellung eines korrosionsgeschützten Stahlblechs zur Beschichtung mit einem organischen Beschichtungsmittel anzugeben, welches sich im Vergleich zum gattungsgleichen Stand der Technik durch eine hervorragende Haftung des organischen Beschichtungsmittels sowie durch einen hohen Korrosionswiderstand auch im beschichteten Zustand des Blechs auszeichnet.In the methods known from the prior art, the expenditure on equipment is high, since not only the heat treatment, but also the subsequent cooling process are to be carried out in an inert gas atmosphere. The invention is therefore based on the object of specifying a method for producing a corrosion-protected steel sheet for coating with an organic coating agent, which in comparison to the generic state of the art by excellent adhesion of the organic coating composition and by a high corrosion resistance in the coated state of the sheet distinguished.

Die Aufgabe wird erfindungsgemäß mit einem Verfahren nach dem Oberbegriff des Patentanspruches 1 dadurch gelöst, dass das Abkühlen mit einem wässrigen Kühlmedium unter normalen Atmosphärenbedingungen erfolgt.The object is achieved by a method according to the preamble of claim 1, characterized in that the cooling is carried out with an aqueous cooling medium under normal atmospheric conditions.

Bei dem erfindungsgemäßen Verfahren wird zunächst in bekannter Weise ein Stahlblech mit einem Überzug aus Zink oder einer Zinklegieriαng versehen. Dies erfolgt in bekannter Weise im Sclnmelztauchverfahren (Feuerverzinkung) oder durch elektrolyt±sche Abscheidung. Im folgenden wird das verzinkte Stahlblech im Vakuum mit einem zusätzlichen Metall beschichtet. Daran schließt sich eine thermische Diffusionsbehandlung an, bei welcher Atome der im Vakuum aufgebrachten Metallschicht in die darunter liegende Zink¬ bzw. Zinklegierungssctiicht hinein diffundieren. Durch den Restgasanteil im Vakuum und während der thermischen Diffusionsbehandlung bildet sich auf der Oberfläche des beschichteten Stahlblechs eine native Oxidschicht aus, welche die Oberfläche passiviert und somit ihren Korrosionswiderstand erhöht. Erfindungsgemäß ist vorgesehen, dass das "veredelte Stahlblech nach der thermischen Diffusionsbehandlung mit einem wässrigen Kühlmedium abgekühlt wird.In the method according to the invention, a steel sheet is first provided in a known manner with a coating of zinc or a Zinklegieriαng. This takes place in a known manner in the melt-dip process (hot-dip galvanizing) or by electrolytic deposition. In the following, the galvanized steel sheet is coated in vacuum with an additional metal. This is followed by a thermal diffusion treatment in which atoms of the metal layer applied in a vacuum diffuse into the underlying zinc or zinc alloy. Due to the residual gas content in the vacuum and during the thermal diffusion treatment, a native oxide layer forms on the surface of the coated steel sheet, which passivates the surface and thus increases its corrosion resistance. According to the invention, it is provided that the "finished steel sheet after the thermal diffusion treatment is cooled with an aqueous cooling medium.

Durch die Verwendung eines einfachen wässrigen Kühlmediums kann der Produktions aufwand und damit die anfallenden Kosten gegenüber dem. aus dem Stand der Technik bekannten Verfahren erheblich reduziert werden. Dabei werden, wie Untersuchungen der A.nmelderin überraschenderweise gezeigt haben, in Bezug auf die Korrosionsbeständigkeit und die Lackhaftung wenigstens gleichwertige Ergebnisse erzielt. Erwartungsgemäß würden sich bei einer Behandlung mit Wasser Oxidationsprobleme einstellen. Überraschenderweise bleiben negative Reaktionen mit dem zusätzlichen Metall aus. Wie sich in weiteren Experimenten der Anmelderin zeigte, kann auf eine der Beschichtung mit einem organischen Beschichtungsmittel vorausgehende, in der Fachwelt für notwendig erachtete Zwischenbehandlung vollständig verzichtet werden. Diese ist im Falle von Mischbauweisen mit konventionellen Produkten aber weiter möglich.By using a simple aqueous cooling medium, the production costs and thus the costs incurred over the. From the prior art known methods are significantly reduced. At the same time, at least as far as corrosion resistance and paint adhesion are concerned, at least equivalent results are achieved, as investigations by the applicant have surprisingly shown. As expected, oxidation problems would occur when treated with water. Surprisingly, negative reactions with the additional metal remain. As has been shown in further experiments by the Applicant, it is possible to completely dispense with an intermediate treatment which is considered necessary in the art for coating with an organic coating agent. However, this is still possible in the case of mixed construction with conventional products.

Dadurch, dass die Abkühlung durch das wässrige Kühlmedium unter normalen Atmosphärenbedingungen erfolgt, ist keine Kapselung der Bearbeitungsstation, an der die Abkühlung erfolgt, bzw. eine Befüllung derselben mit Prozessgas, notwendig.The fact that the cooling is carried out by the aqueous cooling medium under normal atmospheric conditions, no encapsulation of the processing station, where the cooling takes place, or a filling of the same with process gas, is necessary.

Ein weiterer Vorteil der Abkühlung mittels eines wässrigen Kühlmediums liegt darin, dass in Teilbereichen der beschichteten Oberfläche, in denen sich keine native Oxidschicht bildet, d.h. an denen der blanke metallische Überzug freiliegt, Wassermoleküle aus dem Kühlmittel zersetzt werden, wobei sich korrosionsschützende, teilweise schwer lösliche Hydiroxide ausbilden. Diese Hydroxide oder: die bei der nachfolgenden Trocknung daraus entstehenden Oxide verbessern entscheidend die Haftung von organischen Beschichtungen auf der Oberfläche des Stahlblechs.Another advantage of cooling by means of an aqueous cooling medium is that in subregions of the coated surface, in which no native oxide layer is formed, ie where the bare metallic coating is exposed, water molecules are decomposed from the coolant, with anti-corrosive, partially form sparingly soluble hydroxides. These hydroxides or: the resulting oxides in the subsequent drying improve significantly the adhesion of organic coatings on the surface of the steel sheet.

Die im Vakuum auf die verzinkte Blechoberfläche aufgebrachte Schicht kann aus einem oder mehreren Metallen aufgebaut sein. Vorzugsweise werden solche Metalle eingesetzt, welche mit dem Zink der Zink- bzw. Zinklegierungsschichtt Mischphasen bilden. Daraus resultiert eine gute Verbindung beider Schichten, und die Korrosionsfestigkeit wird erhöht. Als besonders geeignet erweisen sich reaktive Metalle, wie Magnesium, Aluminium, Eisen oder Mangan oder deren Legierungen.The applied in vacuum on the galvanized sheet surface layer may be composed of one or more metals. Preferably, those metals are used which form mixed phases with the zinc of the zinc or zinc alloy layer. This results in a good connection of both layers, and the corrosion resistance is increased. Particularly suitable are reactive metals, such as magnesium, aluminum, iron or manganese or their alloys.

Durch eine vorgegebene Temperaturführung im Sinne einer definierten Starttemperatur des veredelten Stahlblechs ziα Beginn der Abkühlung, einer voreingestellten Temperatur des Kühlmediums sowie einer festgelegten Kühldauer kann soworαl die Behandlungszeit verkürzt als auch die Qualität der Korrosionsschutzschicht im Sinne eines höheren Korrosionswiderstandes verbessert werden.By a predetermined temperature control in the sense of a defined starting temperature of the finished steel sheet ziα onset of cooling, a preset temperature of the cooling medium and a specified cooling time soworαl shortening the treatment time and the quality of the corrosion protection layer can be improved in terms of higher corrosion resistance.

Die Starttemperatur des Stahlblechs zu Beginn der Abkühlumg beträgt vorzugsweise 250 bis 35O0C, insbesondere 290 bis 3100C. Die Einstellung der Starttemperatur kann technisch! auf verschiedene Weise erfolgen. So ist die Verwendung von Kühlrollen ebenso möglich, wie der Einsatz einer Gaskühlung. Die Dauer der Abkühlung beträgt dabei vorzugsweise 1 bis LO s. Die Temperatur des Kühlmediums sollte nicht zu hoch, gewählt werden, da in diesem Falle der Metallüberzug des Stahlblechs durch das Kühlmittel stark angegriffen wird. Vorzugsweise sollte die Temperatur des Kühlmittels 42°C nicht übersteigen.The starting temperature of the steel sheet at the beginning of Abkühlumg is preferably 250 to 35O 0 C, in particular 290 to 310 0 C. The setting of the starting temperature can technically! done in different ways. Thus, the use of cooling rolls is just as possible as the use of gas cooling. The duration of the cooling is preferably 1 to LO s. The temperature of the cooling medium should not be set too high, since in this case the metal coating of the steel sheet by the coolant is strong is attacked. Preferably, the temperature of the coolant should not exceed 42 ° C.

Die Endtemperatur des Stahlblechs nach der Abkühlung beträgt vorzugsweise 20 b>is 1200C, insbesondere 40 bis 600C. Dadurch ergibt sich, ein weiter Arbeitsbereich. Eine Erhöhung der Endtemperatur über 12O0C hinaus ist nicht sinnvoll, da es sonst zu einer Schädigung nachfolgender gummierter Rollen für die Entfernung des Kühlmediums kommen kann.The final temperature of the steel sheet after cooling is preferably 20 b> is 120 0 C, in particular 40 to 60 0 C. This results in a wide working range. An increase in the final temperature beyond 12O 0 C addition does not make sense, otherwise it can lead to damage of subsequent rubberized rollers for the removal of the cooling medium.

Um die Ausbildung sichtbarer Muster auf der Oberfläche zu vermeiden, ist es zweckmäßig, das beschichtete Stahlblech unmittelbar zu Beginn der- Abkühlung durch das wässrige Kühlmedium vollständig zu benetzen. Hierzu kann die Abkühlung in einem Tauchbad durchgeführt werden. Ebenso lässt sich das beschichtete Stahlblech auch besprühen, wobei das Aufsprühen vorzugsweise unter Hochdruck erfolgt, da hierbei eine besonders schnelle Kühlung und Passivierrung der Oberfläche erreicht werden kann. Zudem kann bei sehr? heißen Blechoberflächen auf diese Weise die sich unmittelbar an der OberfLäche bildende Wasserdampfschichit, welche den Wärmeübergang zwischen dem Stahlblech und denn Kühlmedium stark herabsetzt, durchbrochen werden (Leidenfrost-Effekt) .In order to avoid the formation of visible patterns on the surface, it is expedient to completely wet the coated steel sheet immediately at the beginning of cooling by the aqueous cooling medium. For this purpose, the cooling can be carried out in a dip. Likewise, the coated steel sheet can also be sprayed, wherein the spraying is preferably carried out under high pressure, since in this case a particularly rapid cooling and Passivierrung the surface can be achieved. Besides, can at very? hot sheet metal surfaces in this way are formed directly on the OberfLäche forming Wasserschampfschichit which greatly reduces the heat transfer between the steel sheet and the cooling medium (Leidenfrost effect).

Sinnvollerweise sollte das wässrige Kühlmedium unmittelbar nach dem Abkühlen von der- Oberfläche des beschichteten Stahlblechs entfernt werden. Hierdurch wird die die Oberfläche des veredelten Stahlblechs überziehende native Oxidschicht stabilisiert. Die Entfernung des Kühlmediums kann beispielsweise durch Abquetschwalzen oder auch durrch einen Gasstrahl erfolgen.It is meaningful that the aqueous cooling medium should be removed immediately after cooling from the surface of the coated steel sheet. As a result, the native oxide layer covering the surface of the finished steel sheet is stabilized. The removal of the cooling medium For example, can be done by squeezing or durrch a gas jet.

Die Korrosionsbeständigkeit und die Haftung der aufzutragenden organischen Beschichtung kann durch weitere Maßnahmen weiter verbessert werden. So können dem wässrrigen Kühlmedium lösliche Salze zugegeben werden. Diese setzen geeignete zweiwertige Metallionen oder Hydroxidionen frrei und verschieben somit das Lösungsgleichgewicht zum undissoziierten Oxid gemäß der GleichungThe corrosion resistance and the adhesion of the organic coating to be applied can be further improved by further measures. Thus, soluble salts can be added to the aqueous cooling medium. These set free suitable divalent metal ions or hydroxide ions and thus shift the solution equilibrium to the undissociated oxide according to the equation

M-Oxid + H2O O M(OH)2 <-> M2+ + 2 OH" M-oxide + H 2 OOM (OH) 2 <-> M 2+ + 2 OH "

M: MetallatomM: metal atom

Dadurch kann die Auflösung der schützenden nativen Oxidschicht vermindert und diese stabilisiert werden.This can reduce the resolution of the protective native oxide layer and stabilize it.

Ebenso können dem wässrigen Kühlmedium puffernde Substanzen, insbesondere Acetat-, Phosphat-, Borat-, Carbonat-, oder Citrat-Ionen, zugegeben werden, durch welche ein optimaler pH-Wert im Sinne einer minimalen Hydrolyse amphoterer nativer Metalloxide eingestellt werden kann. So sollte der pH-Wert weder im schwach sauren Beireich (pH < 5) noch im stark basischen Bereich (pH > 12,5) liegen.Likewise, buffering substances, in particular acetate, phosphate, borate, carbonate, or citrate ions, can be added to the aqueous cooling medium, by means of which an optimum pH in the sense of minimum hydrolysis of amphoteric native metal oxides can be set. Thus, the pH value should be neither in the weakly acidic range (pH <5) nor in the strongly basic range (pH> 12.5).

Durch den Einsatz von Carbonat-Ionen als Puffer-Substanz kann durch die Bildung unlöslicher Carbonate eine zusätzliche Stabilisierung der Blechoberfläche erreicht werden. Die erfindungsgemäß besonders einfache Durchführung des Abkühlschrittes innerhalb der Herstellung korrosionsgeschützter Stahlbleche erlaubt es schließlich ohne weiteres, dass das Stahlblech als Band im Durchlauf beschichtet, diffus!onsbehandelt und gekühlt wird. Dadurch ist das erfindungsgeinäße Verfahren auch für den großtechnischen Betirieb in Bandbeschichtungsanlagen geeignet.Through the use of carbonate ions as a buffer substance, an additional stabilization of the sheet surface can be achieved by the formation of insoluble carbonates. The particularly simple implementation of the cooling step within the production of corrosion-protected steel sheets according to the invention finally makes it readily possible for the steel sheet to be coated as a continuous strip, to be treated in a diffused manner and to be cooled. As a result, the method according to the invention is also suitable for large-scale operation in coil coating systems.

Da infolge der hervorragenden Lackhaftungseigenschaften der Oberfläche eine Zwischenbehandlung des beschichteten, diffusionsbehandelten und anschließend abgekühlten Stahlblechs vor der Auftragung einer organischen Beschichtung nicht mehr notwendig ist, ist es möglich, das organische Beschichtungsmittel unmittelbar nach Entfernung des wässrigen Kühlmediums aufzutragen. Dadurch kann dex Fertigungsprozess erheblich beschleunigt werden, was zυ weiteren Kosteneinsparungen führt.Since, due to the excellent paint adhesion properties of the surface, intermediate treatment of the coated, diffusion-treated and subsequently cooled steel sheet prior to application of an organic coating is no longer necessary, it is possible to apply the organic coating agent immediately after removal of the aqueous cooling medium. As a result, the production process can be considerably accelerated, which leads to further cost savings.

Im folgenden wird die Erfindung anhand einer ein Ausführungsbeispiel darstellenden Zeichnung näher erläutert. Die Zeichnung zeigt eine Anlage zur kontinuierlichen Veredelung und anschließenden Lackieriαng eines Stahlbandes.In the following the invention will be explained in more detail with reference to a drawing illustrating an embodiment. The drawing shows a plant for the continuous refining and subsequent painting of a steel strip.

Gemäß der Zeichnung wird ein Substrat in Form eines Stahlbandes 1 zunächst durch eine oder mehrere Zellen 2 geleitet und in einem elektrolytischen Abscheideprozess mit einer Zinkschicht überzogen. Ebenso ist eine Verzinkung im Schmelztauchverfahren (Feuerverzinkung) möglich. Im Anschluss daran tritt das Stahlband 1 in eine Vakuumkanxmer 3 ein. In dieser wird das Band 1 mit einem aus dem Stand der Technik bekannten Beschichtungsverfahren, beispielsweise mittels PVD, mit einem zusätzlichen Metall, vorzugsweise Magnesium, beschichtet. Weitere einsetzbare Metalle sind beispielsweise Aluminium und Mangan.According to the drawing, a substrate in the form of a steel strip 1 is first passed through one or more cells 2 and coated in a electrolytic deposition process with a zinc layer. Likewise, galvanizing in the hot dip process (hot dip galvanizing) is possible. Subsequently, the steel strip 1 enters a Vakuumkanxmer 3 a. In this the band 1 with one from the state coating technique known in the art, for example by means of PVD, with an additional metal, preferably magnesium coated. Further usable metals are, for example, aluminum and manganese.

Durch das Restgas in der Vakuumkammer 3 wächst auf dem Magnesiumüberzug unverzüglich eine native Oxidschicht auf. Durch Einstellung der Partialdrücke von O2 oder H2O in der Restgasatmosphäre der Vakuumkammer 3 kann diese native Oxidschicht dabei gezielt beeinflusst werden.Due to the residual gas in the vacuum chamber 3 grows on the magnesium coating immediately on a native oxide layer. By adjusting the partial pressures of O 2 or H 2 O in the residual gas atmosphere of the vacuum chamber 3, this native oxide layer can be specifically influenced.

Nach Verlassen der Vakuumkammer 3 tritt das beschichtete verzinkte Stahlband 1 in eine mit einer Heizeinrichtung 4a versehenen Heizkammer 4 ein. In dieser Heizkammer 4 erfolgt sodann eine thermische Diffusionsbehandlung, welche in normaler Atmosphäre durchgeführt werden kann. Im Zuge der Diffusionsbehandlung diffundiert die im Vakuum aufgebrachte Magnesiumschicht teilweise in die darunter liegende Zinkschicht, wobei sich aus Zink und Magnesium bestehende intermetallische Phasen ausbilden.After leaving the vacuum chamber 3, the coated galvanized steel strip 1 enters a heating chamber 4 provided with a heating device 4a. In this heating chamber 4 then takes place a thermal diffusion treatment, which can be carried out in a normal atmosphere. In the course of the diffusion treatment, the magnesium layer applied in a vacuum partially diffuses into the underlying zinc layer, forming intermetallic phases consisting of zinc and magnesium.

Nach Austritt aus der Heizkammer 4 wird das Stahlband 1 an mindestens einer Kühlrolle 5 umgelenkt und wird dabei auf eine definierte Temperatur abgekühlt. Diese ist zugleich die Starttemperatur des sich nun anschließenden Abkühlvorgangs und beträgt vorzugsweise 250 bis 3500C, insbesondere 290 bis 31O0C.After emerging from the heating chamber 4, the steel strip 1 is deflected at least one cooling roller 5 and is thereby cooled to a defined temperature. This is at the same time the starting temperature of the subsequent cooling process and is preferably 250 to 350 0 C, in particular 290 to 31O 0 C.

Zur kontrollierten Abkühlung wird das Stahlband 1 in eine weitere Kammer 6 geleitet. In dieser Kammer, in welcher ebenfalls normale Atmosphärenbedingungen herrschen, wird die diffusionsbehandelte Oberfläche mit einem wässrigen Kühlmedium unter Hochdruck besprüht. Alternativ zum Aufsprühen kann die Abkühlung auch in einem Tauchbad erfolgen. Bei_ dem wässrigen Kühlmedium kann es sich um reines Wasserr handeln. Es können in dem Kühlmedium jedoch auch Salze gelöst sein, welche das Lösungsgleichgewicht zum undissoziierten Oxid verschieben. Ebenso kann das Kühlmedium puffernde Substanzen, beispielsweise Acetat-, Phosphat-, Borat-, Carbonat-, oder Citrat-Ionen, enthalten, durch welche ein optimaler pH-Wert im Sinne einer minimalen Hydrolyse araphoterer nativer Metalloxide eingestellt werden kann.For controlled cooling, the steel strip 1 is passed into a further chamber 6. In this chamber, in which also normal atmospheric conditions prevail, the diffusion-treated surface with an aqueous Spray cooling medium under high pressure. As an alternative to spraying, the cooling can also take place in a dipping bath. Bei_ the aqueous cooling medium may be pure Wasserr act. However, salts which shift the solution equilibrium to the undissociated oxide can also be dissolved in the cooling medium. Likewise, the cooling medium can contain buffering substances, for example acetate, phosphate, borate, carbonate, or citrate ions, by means of which an optimum pH value can be set in the sense of minimal hydrolysis of magnetic native metallic oxides.

Vorzugsweise ist die Sprüheinrichtung derart ausgelegt, dass das beschichtete Stahlblech unmittelbar zu Beginn der Abkühlung durrch das wässrige Kühlmedium vollständig benetzt wird, um die Ausbildung sichtbarer Muster auf der Oberfläche zu vermeiden. Die Abkühlung in der Kammer 6 erfolgt mit einer vorgegebene Temperaturführung. Daloei beträgt die Temperatur des Kühlmediums maximal 420C- Die Einwirkdauer des Kühlmediums auf das Stahlband 1 liegt zwischen 1 und 10 s.Preferably, the spraying device is designed such that the coated steel sheet is completely wetted immediately at the beginning of the cooling by the aqueous cooling medium in order to avoid the formation of visible patterns on the surface. The cooling in the chamber 6 takes place with a predetermined temperature control. Daloei is the temperature of the cooling medium maximum 42 0 C- The exposure time of the cooling medium to the steel strip 1 is between 1 and 10 s.

Unmittelbar nach Austritt aus der Kammer 6 wird das Kühlmedium durch Abquetschrollen 7 von der Bandoberiflache entfernt. Dabei unterstützt die Restwärme des Bandes 1 die Entfernung des Kühlmediums durch Verdampfen. Alternativ kann die Entfernung des Kühlmediums auch durch einen Gasstrahl erfolgen.Immediately after exiting the chamber 6, the cooling medium is removed by squeezing rollers 7 from the Bandoberiflache. The residual heat of the belt 1 supports the removal of the cooling medium by evaporation. Alternatively, the removal of the cooling medium can also be effected by a gas jet.

Sodann kann das trockene Stahlband 1 ohneThen, the dry steel strip 1 without

Zwischenbehandlung einer Lackiereinheit 8 zugeführt werden, welche in einem kontinuierlichen Walzlackierprozess das Stahlband 1 in-line beschichtet. Wahlweise kann die Lackierung auch ex-line mittels Walzlackierrprozess, Sprüh¬ oder Tauchlackierung erfolgen. Intermediate treatment of a coating unit 8 are fed, which in a continuous Walzlackierprozess the Steel strip 1 coated in-line. Optionally, the coating can also be done ex-line by Walzlackierrprozess, spray or dip.

Claims

P A T E N T A N S P R U C H E PATENT CLAIMS 1. Verfahren zum Herstellen eines korrosionsgeschützten Stahlblechs (1) zur Beschich"tung mit einem organischen Beschichtungsmittel, bei dem das mit einem Überzug aus Zink oder einer Zinklegierung korrosionsgeschützte Stahlblech im Vakuum mit mindestens einem zusätzlichen Metall oder einer Metalllegierung beschichtet, anschließend einer thermischen Diffusionsbehandlung unterworfen und abschließend abgekühlt wird, d a d u r c h g e k e n n z e i c h n e t, d a s s das Abkühlen mit einem wässrigen Kühlmedium unter normalen Atmosphärenbedingungen erfolgt.1. A method of producing a corrosion-protected steel sheet (1) for coating with an organic coating agent in which the coated with a coating of zinc or a zinc alloy corrosion-protected steel sheet in vacuum with at least one additional metal or a metal alloy, then subjected to a thermal diffusion treatment and finally cooling, characterized in that the cooling is carried out with an aqueous cooling medium under normal atmospheric conditions. 2. Verfahren nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t, d a s s das mindestens eine zusätzli che Metall mit Zink eine Mischphase bildet.2. The method of claim 1, wherein: at least one additional metal with zinc forms a mixed phase. 3. Verfahren nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t, d a s s das mindestens eine zusätzliche Metall ein Metall der Gruppe Mg, Al, Mn ist bzw. dass die Metalllegierung aus wenigstens zwei Metallen dieser Gruppe gebildet ist.3. The method according to claim 1 or 2, wherein the at least one additional metal is a metal of the group Mg, Al, Mn or that the metal alloy is formed from at least two metals of this group. 4. Verfahren nach einem der Ansprüche 1 bis 3, d a d u r c h g e k e n n z e i c h n e t, d a s s die Abkühlung mit einer vorgegeben Temperaturführung erfolgt.4. The method according to any one of claims 1 to 3, characterized in that the cooling takes place with a predetermined temperature control. 5. Verfahren nach einem der Ansprüche 1 bis 4, d a d u r c h g e k e n n z e i c h n e t, d a s s die Starttemperatur des Stahlblechs zu Beginn der Abkühlung 250 bis 3500C, vorzugsweise 290 bis 31O0C, beträgt.5. The method according to any one of claims 1 to 4, characterized in that the starting temperature of the steel sheet at the beginning of the cooling 250 to 350 0 C, preferably 290 to 31O 0 C, is. 6. Verfahren nach einem der Anspüche 1 bis 5, d a d u r c h g e k e n n z e i c h n e t, d a s s die Starttemperatur der Abkühlung mittels Kühlrollen (5) eingestellt wird.6. The method according to any one of claims 1 to 5, wherein a starting temperature of cooling by means of cooling rollers (5) is set. 7. Verfahren nach einem der Anspüche 1 bis 5, d a d u r c h g e k e n n z e i c h n e t, d a s s die Starttemperatur der Abkühlung mittels einer Gaskühlung eingestellt wird.7. Method according to one of the claims 1 to 5, wherein a starting temperature of the cooling is set by means of gas cooling. 8. Verfahren nach einem der Ansprüche 1 bis 6, d a d u r c h g e k e n n z e i c h n e t, d a s s die Dauer der Abkühlung 1 bis 10 s beträgt.8. A process according to any one of claims 1 to 6, wherein the duration of the cooling is from 1 to 10 sec. 9. Verfahren nach einem der Ansprüche 1 bis 8, d a d u r c h g e k e n n z e i c h n e t, d a s s die Temperatur des wässrigen Kühlmediums maximal 420C beträgt.9. The method according to any one of claims 1 to 8, characterized in that the temperature of the aqueous cooling medium is at most 42 0 C. 10. Verfahren nach einem der Anspüche 1 bis 9, d a d u r c h g e k e n n z e i c h n e t, d a s s die Endtemperatur zum Ende der Abkühlung 20 bis 1200C, vorzugsweise 40 bis 60°C, beträgt.10. The method according to any one of Anspüche 1 to 9, characterized in that the final temperature at the end of the cooling 20 to 120 0 C, preferably 40 to 60 ° C, is. 11. Verfahren nach einem der Ansprüche 1 bis 10, d a d u r c h g e k e n n z e i c h n e t, d a s s das beschichtete Stahlblech unmittelbar zu Beginn der Abkühlung durch das wässrige Kühlmedium vollständig benetzt wird.11. A process according to any one of claims 1 to 10, wherein the coated steel sheet is completely wetted by the aqueous cooling medium immediately at the beginning of the cooling. 12. Verfahren nach einem der Ansprüche 1 bis 11, d a d u r c h g e k e n n z e i c h n e t, d a s s die Abkühlung in einem Tauchbad erfolgt .12. The process according to claim 1, wherein the cooling takes place in a dipping bath. 13. Verfahren nach einem der Ansprüche 1 bis 11, d a d u r c h g e k e n n z e i c h n e t, d a s s die Abkühlung durch Besprühen erfolgt.13. A process according to any one of claims 1 to 11, wherein said cooling is by spraying. 14. Verfahren nach Anspruch 13, d a d u r c h g e k e n n z e i c h n e t, d a s s das wässrige Kühlmedium unter Hochdruck aufgesprüht wird.14. The process of claim 13, wherein the aqueous cooling medium is sprayed on under high pressure. 15. Verfahren nach einem der Ansprüche 1 bis 14, d a d u r c h g e k e n n z e i c h n e t, d a s s das wässrige Kühlmedium unmittelbar nach dem Atokühlen von der Oberfläche des beschichteten Stahlblecϊis entfernt wird.15. The process according to claim 1, wherein the aqueous cooling medium is removed from the surface of the coated steel sheet immediately after the atcooling. 16. Verfahren nach Anspruch 15, d a d u r c h g e k e n n z e i c h n e t, d a s s das wässrige Kühlmedium durch Abquetschwalzen (7) entfernt wird. 16. The method according to claim 15, characterized in that the aqueous cooling medium by squeezing rollers (7) is removed. 17. Verfahren nach Anspruch 15, d a d u r c h g e k e n n z e i c h n e t, d a s s das wässrige Kühlmedium durch einen Gasstrahl entfernt wird.17. The method of claim 15, wherein the aqueous cooling medium is removed by a gas jet. 18. Verfahren nach einem der Ansprüche 1 bis 17, d a d u r c h g e k e n n z e i c h n e t, d a s s das wässrige Kühlmedium lösliche Salze enthält, die zweiwertige Metallionen oder Hydroxid — Ionen freisetzen, welche das Lösungsgleichgewicht zum undissoziierten Ox-Ld verschieben.18. The method according to any one of claims 1 to 17, wherein the aqueous cooling medium contains soluble salts which release divalent metal ions or hydroxide ions which shift the solution equilibrium to the undissociated Ox-Ld. 19. Verfahren nach einem der Ansprüche 1 3ois 18, d a d u r c h g e k e n n z e i c h n e t, d a s s das wässrige Kühlmedium puffernde Substanzen enthält.19. The method of claim 1, wherein the aqueous cooling medium contains buffering substances. 20. Verfahren nach Anspruch 19, d a d u r c h g e k e n n z e i c h n e t, d a s s das wässrige Kühlmedium als puffernde Substanzen Acetat-, Phosphat-, Borat-, Carbonat- , oder Citrat- Ionen enthält.20. Method according to claim 19, wherein the aqueous cooling medium contains acetate, phosphate, borate, carbonate, or citrate ions as buffering substances. 21. Verfahren nach einem der Ansprüche 1 bis 20, d a d u r c h g e k e n n z e i c h n e t, d a s s das Stahlblech als Band im Durchlauf beschichtet, diffusionbehandelt und gekühlt wird.21. Method according to one of claims 1 to 20, wherein the steel sheet is coated as a strip in a continuous flow, is diffusion-treated and cooled. 22. Verfahren nach einem der Ansprüche 1 bis 21, d a d u r c h g e k e n n z e i c h n e t, d a s s das organische Beschichtungsmittel nach Entfernung des wässrigen Kühlmediums ohne Zwischenbehandlung aufgetragen wird. 22. The process as claimed in any of claims 1 to 21, wherein the organic coating composition is applied after removal of the aqueous cooling medium without intermediate treatment.
PCT/EP2005/011387 2004-10-28 2005-10-24 Method for producing a steel sheet protected against corrosion Ceased WO2006045570A1 (en)

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EP05796770A EP1805342A1 (en) 2004-10-28 2005-10-24 Method for producing a steel sheet protected against corrosion
JP2007538319A JP2008518100A (en) 2004-10-28 2005-10-24 Method of manufacturing a corrosion-protected steel sheet
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